US2839582A - Ethers of chlorinated and fluorinated phenols - Google Patents
Ethers of chlorinated and fluorinated phenols Download PDFInfo
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- US2839582A US2839582A US465765A US46576554A US2839582A US 2839582 A US2839582 A US 2839582A US 465765 A US465765 A US 465765A US 46576554 A US46576554 A US 46576554A US 2839582 A US2839582 A US 2839582A
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- ether
- ethers
- bromide
- myristyl
- tetradecyl
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- 150000002170 ethers Chemical class 0.000 title claims description 11
- 150000002989 phenols Chemical class 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims description 12
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-UHFFFAOYSA-N 0.000 claims description 6
- 150000005215 alkyl ethers Chemical class 0.000 claims description 4
- LHJGJYXLEPZJPM-UHFFFAOYSA-N 2,4,5-trichlorophenol Chemical compound OC1=CC(Cl)=C(Cl)C=C1Cl LHJGJYXLEPZJPM-UHFFFAOYSA-N 0.000 claims description 3
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 claims description 3
- NVWVWEWVLBKPSM-UHFFFAOYSA-N 2,4-difluorophenol Chemical compound OC1=CC=C(F)C=C1F NVWVWEWVLBKPSM-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 230000004071 biological effect Effects 0.000 claims description 2
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical compound OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-UHFFFAOYSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 27
- -1 aliphatic ethers Chemical class 0.000 description 25
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- SRCKKPZXOUZSTQ-UHFFFAOYSA-N 2,4-dichloro-1-tetradecoxybenzene Chemical compound CCCCCCCCCCCCCCOC1=CC=C(Cl)C=C1Cl SRCKKPZXOUZSTQ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 235000013399 edible fruits Nutrition 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000001350 alkyl halides Chemical class 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HNTGIJLWHDPAFN-UHFFFAOYSA-N 1-bromohexadecane Chemical compound CCCCCCCCCCCCCCCCBr HNTGIJLWHDPAFN-UHFFFAOYSA-N 0.000 description 3
- KOFZTCSTGIWCQG-UHFFFAOYSA-N 1-bromotetradecane Chemical compound CCCCCCCCCCCCCCBr KOFZTCSTGIWCQG-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 240000003768 Solanum lycopersicum Species 0.000 description 3
- 239000004009 herbicide Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 2
- NGYRHCVFBFVZBQ-UHFFFAOYSA-N 1-chloro-4-tetradecoxybenzene Chemical compound CCCCCCCCCCCCCCOC1=CC=C(Cl)C=C1 NGYRHCVFBFVZBQ-UHFFFAOYSA-N 0.000 description 2
- GJIGWEGYZKMMTH-UHFFFAOYSA-N 2,4-dichloro-1-octoxybenzene Chemical compound CCCCCCCCOC1=CC=C(Cl)C=C1Cl GJIGWEGYZKMMTH-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 235000002566 Capsicum Nutrition 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 240000004244 Cucurbita moschata Species 0.000 description 2
- 235000009854 Cucurbita moschata Nutrition 0.000 description 2
- 235000009852 Cucurbita pepo Nutrition 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000006002 Pepper Substances 0.000 description 2
- 235000016761 Piper aduncum Nutrition 0.000 description 2
- 235000017804 Piper guineense Nutrition 0.000 description 2
- 244000203593 Piper nigrum Species 0.000 description 2
- 235000008184 Piper nigrum Nutrition 0.000 description 2
- 244000061458 Solanum melongena Species 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 230000036512 infertility Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000008635 plant growth Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Inorganic materials [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 2
- 235000020354 squash Nutrition 0.000 description 2
- ZESPQVWXKMIMBM-UHFFFAOYSA-N 1-(2,4-difluorophenoxy)-2,4-difluorobenzene Chemical compound FC1=CC(F)=CC=C1OC1=CC=C(F)C=C1F ZESPQVWXKMIMBM-UHFFFAOYSA-N 0.000 description 1
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 description 1
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 1
- GTIYWLZJQXTEGU-UHFFFAOYSA-N 1-chloro-4-dodecoxybenzene Chemical compound CCCCCCCCCCCCOC1=CC=C(Cl)C=C1 GTIYWLZJQXTEGU-UHFFFAOYSA-N 0.000 description 1
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 description 1
- DAGHOJGVSBRNPO-UHFFFAOYSA-N 1-dodecoxy-4-fluoro-2-methylbenzene Chemical compound CCCCCCCCCCCCOC1=CC=C(F)C=C1C DAGHOJGVSBRNPO-UHFFFAOYSA-N 0.000 description 1
- VIPWUFMFHBIKQI-UHFFFAOYSA-N 1-fluoro-4-methoxybenzene Chemical compound COC1=CC=C(F)C=C1 VIPWUFMFHBIKQI-UHFFFAOYSA-N 0.000 description 1
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 description 1
- PCIMUOSXKOWDPO-UHFFFAOYSA-N 2,4-dichloro-1-decoxybenzene Chemical compound CCCCCCCCCCOC1=CC=C(Cl)C=C1Cl PCIMUOSXKOWDPO-UHFFFAOYSA-N 0.000 description 1
- SOFLFNMEOFJEKN-UHFFFAOYSA-N 2,4-difluoro-1-tetradecoxybenzene Chemical compound CCCCCCCCCCCCCCOC1=CC=C(F)C=C1F SOFLFNMEOFJEKN-UHFFFAOYSA-N 0.000 description 1
- GKQDDKKGDIVDAG-UHFFFAOYSA-N 4-fluoro-2-methylphenol Chemical compound CC1=CC(F)=CC=C1O GKQDDKKGDIVDAG-UHFFFAOYSA-N 0.000 description 1
- 240000001592 Amaranthus caudatus Species 0.000 description 1
- 235000009328 Amaranthus caudatus Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000232088 Setaria <nematode> Species 0.000 description 1
- 235000017016 Setaria faberi Nutrition 0.000 description 1
- 240000005498 Setaria italica Species 0.000 description 1
- 235000007226 Setaria italica Nutrition 0.000 description 1
- 241000820191 Setaria magna Species 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 125000004188 dichlorophenyl group Chemical group 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000005648 plant growth regulator Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Definitions
- This invention relates to the control of plant growth by long-chain aliphatic ethers of chlorinated and fluorinated phenols. It also relates to certain new compounds in this group. i
- halogenated phenyl alkyl ethers are effective as plant growth regulators, functioning as herbicides and also in the production of sterility. They may also be employed to prevent premature drop of fruit.
- ethers which we have found to be effective have straight alkyl chains containing even numbers of carbon atoms. They are further characterized as follows:
- the ethers are applied in the same manner as, but are less active than 2,4-D. Due to their low solubility in water, they are preferably emulsified by the use of suitable emulsifying agents. Since they have densities near that of water they produce stable emulsions.
- novel compounds are the alkyl ethers of 2,4-dichlo-rophenol having an even number of carbon atoms in a straight alkyl chain containing from eight to eighteen carbon atoms, 2,4,5- trichlorophenyl n-hexadecyl ether, 4-fluorophenyl n-dodecyl ether, 4-fluorophenyl n-tetradecyl ether, 2,4-difluorophenyl n-dodecyl ether, and the n-dodecyl, n-tetradecyl, and n-hexadecyl ethers of 2-methyl-4-i lu orophenol.
- the new ethers. are oils or crystalline solids somewhat soluble in many organic solvents such as hydrocarbons, alcohols, ethers, ketones, etc., and practically insoluble in water. They are stable to light, air, and carbon dioxide, and have low volatilities. They areuseful in the control of the growth of plants, as described above, and as intermediates in the preparation of more complex organic derivatives.
- the compounds may be prepared by reacting (1) at least a molecular proportion of the proper chlorinated or fluorinated phenol as the sodium salt thereof, and (2) a molecular proportion of an alkyl halide such as octyl chloride, myristyl bromide, cetyl bromide, etc., or any similar halogenated derivative of an alkane bearing the desired alkyl group carbon atoms.
- the reaction is carried, out in the presence of a solvent such as absolute ethanol.
- a catalyst such as sodium or potassium iodide may be used to facilitate halogen interchange and increase the yield of the ether by preventing dehydrohalogcnation of the alkyl halide to the corresponding alkene.
- the sodium is dissolved in absolute ethanol and an equivalent amount of the phenol is added to form the sodium phenolate. Potassium iodide is then added and dissolved, followed by an equimolecular amount of the alkyl halide. The mixture is then refluxed for 12 hours or longer. The reaction mixture is diluted with water and the ether separates out. The aqueous-alcoholic layer is extracted with a suitable solvent, the extract combined with the precipitated ether and the resulting solution washed with aqueous alkali to remove unreacted phenol and then with water to remove residual salts and alkali. After drying the extract, the solvent is evaporated, leaving behind a liquid or solid other which can be purified by distillation at reduced pressure or recrystallized from a suitable medium, as dictated by its physical properties.
- EXAMPLE III 10.2 grams of 2,4-dichlorophenol was dissolved in 20 milliliters of absolute ethanol. To this was added a solution of 1.4 grams of sodium metal dissolved in 60 milliliters of absolute ethanol. A solution of 9.0 grams of potassium iodide in milliliters of absolute ethanol was added and the mixture refluxed 15 minutes. 20 grams of myristyl bromide was then added and the resulting mixture refluxed 36 hours on a steam bath.
- a chemical compound possessing biological activity selected from the group consisting of: alkyl ethers of 2,4- dichlor'ophenol having an even number of carbon atoms in the range 8 to 18 in a straight chain in the alkyl group; the n-hexadecyl ether of 2,4,5-trichlorophenol, the ndodecyl, n-tetradecyl and n-hexadecyl ethers of i -fluorophenol, the n-dodecyl, n-tetradecyl and n-hexadecyl ethers of 2,4-difluorophenol and the n-dodecyl, n-tetradecyl and n-hexadecyl ethers of 2-methyl-4-fluorophenol.
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States Patent ETHERS OF CHLORINATED AND FLUORINATED PHENOLS William L. Howard, Stanley R. McLane, Jr., and Robert Weintraub, Frederick, Md.
No Drawing. Application October 29, 1954 Serial No. 465,765
17 Claims. (Cl. 260-612) (Granted under Title 35, U. S. Code (1952), see. 266) The invention described herein may be manufactured and used by or for the Government of the United States of America for governmental purposes without the payment to us of any royalty thereon.
This invention relates to the control of plant growth by long-chain aliphatic ethers of chlorinated and fluorinated phenols. It also relates to certain new compounds in this group. i
We have found that certain halogenated phenyl alkyl ethers are effective as plant growth regulators, functioning as herbicides and also in the production of sterility. They may also be employed to prevent premature drop of fruit.
The ethers which we have found to be effective have straight alkyl chains containing even numbers of carbon atoms. They are further characterized as follows:
Phenolic group:
p Aliphatic chain, carbon atoms 4-chlorophenyl Of these compounds, the group consisting of 4-chlorophenyl myristyl ether, 2,4dichlorophenyl myristyl ether and 2,4-dichlorophenyl cetyl ether have outstanding activity. 2,4dichlorophenyl myristyl ether is the mostactive of all.
in comparison to the well known herbicide 2,4.-dichloropheuoxy acetic acid (2,4--D), these compounds possess distinctive properties in that they give a delayed action which is spread over along period of time, giving a greater over all effect when used in herbicidal quantities. When used in sub-lethal quantities the action, as in production of seedless fruit, is more gradual and produces fewer objectionable side efifects. As herbicides, the ethers are applied in the same manner as, but are less active than 2,4-D. Due to their low solubility in water, they are preferably emulsified by the use of suitable emulsifying agents. Since they have densities near that of water they produce stable emulsions. They may also be used as solutions in alcohols, glycol ethers, etc. Other growth regulating properties are illustrated by the following experiments EXAMPLE I Field grown tomato, pepper, squash, and eggplant plants were sprayed with 2,4 dichlorophenyl tetradecyl ether at rates of 0.1 and 0.5 pound per acre. Seedless fruit was produced in each case. The seedless tomatoes were quite firm and were not as puffy as some seedless fruit. Tomato yields were not reduced. The eggplant was normal both in form and in yield. Pepper yields were not reduced but the fruit was flattened and not of normal shape. Squash was of abnormal shape.
2,839,582 Patented June 17, 1958 2 EXAMPLE II Setaria italica was sprayed with 4-chlorphenyl dodecyl ether and 4-chlorophenyl tetradecyl ether at the rate of 1 pound per acre, producing sterility. This suggests the use of these ethers for reducing the amount of seed produced by foxtail and giant foxtail, both of which are Setaria species, as a means of controlling the spread of these weeds.
Of the compounds which we have found to be useful, a considerable number are new and our invention also embraces these new compounds. These novel compounds are the alkyl ethers of 2,4-dichlo-rophenol having an even number of carbon atoms in a straight alkyl chain containing from eight to eighteen carbon atoms, 2,4,5- trichlorophenyl n-hexadecyl ether, 4-fluorophenyl n-dodecyl ether, 4-fluorophenyl n-tetradecyl ether, 2,4-difluorophenyl n-dodecyl ether, and the n-dodecyl, n-tetradecyl, and n-hexadecyl ethers of 2-methyl-4-i lu orophenol. The new ethers. are oils or crystalline solids somewhat soluble in many organic solvents such as hydrocarbons, alcohols, ethers, ketones, etc., and practically insoluble in water. They are stable to light, air, and carbon dioxide, and have low volatilities. They areuseful in the control of the growth of plants, as described above, and as intermediates in the preparation of more complex organic derivatives.
The compounds may be prepared by reacting (1) at least a molecular proportion of the proper chlorinated or fluorinated phenol as the sodium salt thereof, and (2) a molecular proportion of an alkyl halide such as octyl chloride, myristyl bromide, cetyl bromide, etc., or any similar halogenated derivative of an alkane bearing the desired alkyl group carbon atoms. The reaction is carried, out in the presence of a solvent such as absolute ethanol. A catalyst such as sodium or potassium iodide may be used to facilitate halogen interchange and increase the yield of the ether by preventing dehydrohalogcnation of the alkyl halide to the corresponding alkene.
In the preferred method of preparation, the sodium is dissolved in absolute ethanol and an equivalent amount of the phenol is added to form the sodium phenolate. Potassium iodide is then added and dissolved, followed by an equimolecular amount of the alkyl halide. The mixture is then refluxed for 12 hours or longer. The reaction mixture is diluted with water and the ether separates out. The aqueous-alcoholic layer is extracted with a suitable solvent, the extract combined with the precipitated ether and the resulting solution washed with aqueous alkali to remove unreacted phenol and then with water to remove residual salts and alkali. After drying the extract, the solvent is evaporated, leaving behind a liquid or solid other which can be purified by distillation at reduced pressure or recrystallized from a suitable medium, as dictated by its physical properties.
As an illustration of the method of preparation, the production of myristyl 2,4-dichlorophenyl ether will be described. As has been previously pointed out, this compound is the most active for our purposes of all of the compounds of our group. The other ethers are prepared in a similar manner.
EXAMPLE III 10.2 grams of 2,4-dichlorophenol was dissolved in 20 milliliters of absolute ethanol. To this was added a solution of 1.4 grams of sodium metal dissolved in 60 milliliters of absolute ethanol. A solution of 9.0 grams of potassium iodide in milliliters of absolute ethanol was added and the mixture refluxed 15 minutes. 20 grams of myristyl bromide was then added and the resulting mixture refluxed 36 hours on a steam bath.
After cooling the reaction mixture it was diluted with 500 milliliters of water, then extracted with 300 mil- 3. liliters of ethyl ether in 100 milliliter portions. The ether extract was separated and Washed With 100 milliliters of sodium hydroxide solution, then 300 milliliters of water, again separated and dried over anhy- 4 n-Octyl 2,4-dichlorophenyl ether. n-Decyl 2,4-dichloropheny1 ether. Lauryl 2,4-dichlorophenyl ether. Myristyl 2,4-dichlorophenyl ether.
oetadecyl bromide cetyl bromide lauryl bromide.
do 2,4,5 trichlorophenol. 4 fiugrophenol cetyl bromide octadccyl 2,4 dichlorophenyl ether cetyl 2,4,5 triehlorophenyl ether lauryl 4 fluorophenyl ether myristyl bromide. myristyl 4 fluorophenyl ether cetyl bromide cetyl 4 fluorophenyl etherlauryl bromide lauryl 2,4 difiuorophenyl ethermyristyl bromide. myrsityl 2,4 difluorophenyl ether. cetyl bromide eetyl 2,4 difluorophonyl ether lauryl bromide. lauryl 2 methyl 4 fluorophenyl ether... myristyl bromide. myristyl 2 methyl 4 flluorophenyl ethe eetyl 2 methyl 4 fluorophenyl ether drous sodium sulfate. 5 Cetyl 2,4-dichloropheny1 ether.
The ethyl ether Was removed by distillation leaving Cetyl 2,4,5-trichlorophenyl ether. behind a solid which was crystallized from any suitable Lauryl 4-fluorophenyl ether.
solvent, such as ether or ligro'ine giving White crystals of 10. Myristyl 4-fluorophenyl ether. 2,4-dichlorophenyl myristyl ether melting at 33-34 C., 11. Cetyl 4-fiuorophenyl ether. and having carbon and hydrogen contents of 66.56% and 12. Lauryl 2,4-difluorophenyl ether.
8.85% respectively. For C I-I Cl O the theoretical 13. Myristyl 2,4-difluorophenyl ether. values are 66.84% and 8.98% respectively. 14. Cetyl 2,4-difiuorophenyl ether.
Representative ethers of our group that have been pre- 15. Lauryl 2-methyl-4-fluorophenyl ether. pared by the method described above, and the reactants 16. Myristyl 2-methyl-4-fluorophenyl ether. employed, are shown in Table I. 15 17. Cetyl 2-methyl-4-fluorophenyl ether.
Table I Reactants Boiling Point Melting Ether Product Point, [nln Density O. Temp., Pressure, 0. Alkyl Halide Phenol O. mm. Hg
abs.
1: octyl bromide 2,4 diehlorophenol n octyl 2,4 dichlorophenyl ether n decyl bromide do n decyl 2,4 dichlorophenyl ether.. lauryl bromide do lauryl 2,4 diehlorophenyl ethermyristyl bromide do my1-isty12,4 dichlorophenyl eth cetylbromidenn do eet v12,4diehlorophenylethen-..
While we have described our compounds, their propstood that a number of variations are possible. We therefore desire our invention to be limited solely by the scope of the appended claims.
We claim:
1. A chemical compound possessing biological activity selected from the group consisting of: alkyl ethers of 2,4- dichlor'ophenol having an even number of carbon atoms in the range 8 to 18 in a straight chain in the alkyl group; the n-hexadecyl ether of 2,4,5-trichlorophenol, the ndodecyl, n-tetradecyl and n-hexadecyl ethers of i -fluorophenol, the n-dodecyl, n-tetradecyl and n-hexadecyl ethers of 2,4-difluorophenol and the n-dodecyl, n-tetradecyl and n-hexadecyl ethers of 2-methyl-4-fluorophenol.
' 2. An alkyl ether of 2,4-dichloropheno1 having in the alkyl group an even number of carbon atoms in the range of 8 to 18 in a straight chain.
References Cited in the file of this patent UNITED STATES PATENTS 2,054,509 Pastac Sept. 15, 1936 40 2,137,784 Prutton et al. Nov. 22, 1938 2,188,734 CarsWel1 Jan. 30, 1940 2,327,338 Carswell Aug. 24, 1943 2,581,972 Rottschaefer Ian. 8, 1952 2,594,935 Ladd et al. Apr. 29, 1952 OTHER REFERENCES Jones: Journal, Chemical Society (London), 1935, pp. 1831-5.
McLane et al.: Weeds, vol. II, October 1953, No. 4,
Claims (1)
1. A CHEMICAL COMPOUND POSSESSING BIOLOGICAL ACTIVITY SELECTED FROM THE GROUP CONSISTING OF: ALKYL ETHERS OF 2,4DICHLOROPHENOL HAVING AN EVEN NUMBER OF CARBON ATOMS IN THE RANGE 8 TO 18 IN A STRAIGHT CHAIN IN THE ALKYL GROUP; THE N-HEXADECYL ETHER OF 2,4,5-TRICHLOROPHENOL, THE NDODECYL, N-TETRADECYL AND N-HEXADECYL ETHERS OF 4-FLUOROPHENOL, THE N-DODECYL, N-TETRADECYL AND N-HEXADECYL ETHERS OF 2,4-DIFLUOROPHENOL AND THE N-DODECYL, N-TETRADECYL AND N-HEXADECYL ETHERS OF 2-METHY-4-FLUOROPHENOL.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US465765A US2839582A (en) | 1954-10-29 | 1954-10-29 | Ethers of chlorinated and fluorinated phenols |
| US71810758 US2937935A (en) | 1954-10-29 | 1958-02-13 | Plant growth control by use of ethers of chlorinated and fluorinated phenols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US465765A US2839582A (en) | 1954-10-29 | 1954-10-29 | Ethers of chlorinated and fluorinated phenols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2839582A true US2839582A (en) | 1958-06-17 |
Family
ID=23849067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US465765A Expired - Lifetime US2839582A (en) | 1954-10-29 | 1954-10-29 | Ethers of chlorinated and fluorinated phenols |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2839582A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1184349B (en) * | 1961-09-02 | 1964-12-31 | Lentia Gmbh | Process for the preparation of dichlorophenyl monoisoalkyl ethers |
| FR2592038A1 (en) * | 1985-12-19 | 1987-06-26 | Seiko Epson Corp | CHIRAL ETHERPHENYLIC COMPOUND |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2054509A (en) * | 1932-06-04 | 1936-09-15 | Pastac Isaac | Method for the selective destruction of weeds |
| US2137784A (en) * | 1937-12-29 | 1938-11-22 | Lubri Zol Dev Corp | Lubricant and method of lubricating |
| US2188734A (en) * | 1938-03-24 | 1940-01-30 | Monsanto Chemicals | Selective herbicide |
| US2327338A (en) * | 1939-12-13 | 1943-08-24 | Monsanto Chemicals | Insect control |
| US2581972A (en) * | 1948-12-22 | 1952-01-08 | Gen Aniline & Film Corp | Preparation of 2-chloro-4-methoxy-5-nitro-toluene and 2-chloro-4-methoxy-5-aminotoluene |
| US2594935A (en) * | 1948-04-08 | 1952-04-29 | Us Rubber Co | Dihalogeno propenyl aryl ethers |
-
1954
- 1954-10-29 US US465765A patent/US2839582A/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2054509A (en) * | 1932-06-04 | 1936-09-15 | Pastac Isaac | Method for the selective destruction of weeds |
| US2137784A (en) * | 1937-12-29 | 1938-11-22 | Lubri Zol Dev Corp | Lubricant and method of lubricating |
| US2188734A (en) * | 1938-03-24 | 1940-01-30 | Monsanto Chemicals | Selective herbicide |
| US2327338A (en) * | 1939-12-13 | 1943-08-24 | Monsanto Chemicals | Insect control |
| US2594935A (en) * | 1948-04-08 | 1952-04-29 | Us Rubber Co | Dihalogeno propenyl aryl ethers |
| US2581972A (en) * | 1948-12-22 | 1952-01-08 | Gen Aniline & Film Corp | Preparation of 2-chloro-4-methoxy-5-nitro-toluene and 2-chloro-4-methoxy-5-aminotoluene |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1184349B (en) * | 1961-09-02 | 1964-12-31 | Lentia Gmbh | Process for the preparation of dichlorophenyl monoisoalkyl ethers |
| FR2592038A1 (en) * | 1985-12-19 | 1987-06-26 | Seiko Epson Corp | CHIRAL ETHERPHENYLIC COMPOUND |
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